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Патент USA US2269485

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3m. E3, E942.
V.V A. SÀLMI
2,269,485
PROCESS l'ï‘OR THE CONVERSION OF ASPHALTIC HYDROCARBONS
Filed Jan. 9, 1940
F04 THR FIRM
,4free/vars.
Patent-ed Jan. lf3,
UNITED STATES ~lui'rlazrn‘ oFFicEf
PROCESS FOR THE CONVERSION Y0F l
ASP-BALTIC HYDROCARBONS
.
Y
vaines. salmi, Culver city, cam., [email protected] ,to
Metallytic Corporation, Los Angeles,` Calif., a,
Application
corporation Januar-ys,
ofCalifornia
1940,
- sei-alim.
"
_ 313,034
` '
» >`¿
1o claims.. gorras-1o)
v ‘y
`
’_
l
l' VAl simple, economical process-fori vthe -complet
This invention relates tothe conversion,"of>
»sphalt or asphalt-like hydrocarbons into hydrir'Ã`l` ' conversion -of asphaltic bodies’ lntoâollsg-offî'thef
:arbon oils falling within the boiling point range ' "lubricating oil boiling point range,j-'byf.a.'g-~simple
»t lubricating oils; this conversion being accom
, heat treatment 'without the‘use of :hydrogenëarid-V
nlished by a simple heat treatment, without the
»dditionof hydrogen'or use of chemicals.` 'I'hese
without.y any appreciable loss or'vi'ormation` of fany.
undesirable- by-products, would.t.herefore-'be„v`al
lsphaltic hydrocarbons occurv in nature either
uable, not only froml 'the‘vievvpointfofflubricating.i
is -such or together with lighter hydrocarbons ’ , -' values, b_ut also from the'vieWpOintof»'overcom-'
n petroleum, also in the'destructive distillation ' _ingrefining diñiculties and reducing theare'finingl
»roducts of coal, shale, peat, wood, etc. In such 10 losses and from'the viewpoint oflproducingysuwï
»roducts and especially in petroleum, asphaltlc '
»odies form the least valuable constituent- and
Derior fuel oils'andmore desirable`- tocks'for.
i cracking operations;
n the refining of such products for variousl in
Y
I
it is an objectA of my inventionrto :rovideca:
lustrial uses', the asphalt presents one ‘of the
method of - simple and'eilicient. character ,wherea
,Teatest problems not only from a purely techni-A 15 "by vheavy hydrocarbons may >'be Íconverted pinto;y
1al, but also from a commercial viewpoint.
lighter hydrocarbons and-'whereby-a‘substantial
l
Thus, in the separation of the various constit
conversión yof ‘asphalt or asphalt-like'íresidues *_
j
lents of petroleum by distillation, not only are
he asphaltic bodies separated with diillculty '
into
treatment,
hon conversion
lubricating.
and in
method
>ofilqn‘iay
generalbe
for
toobtained-by
the'manufacturexotr4
provide la-»hydrocarv
pyrolytic '~ f .
rom the most valuable fractions; that is, the
ieavy lubricating oils, but the tendency is for
lubricating
stocks of superior
oils, fuel
quality.
oils, or overhead
.
« '_ cracking
'
he lubricating Voil fractions to revert >into
lsphalt. Moreover, the asphaltic residues may
If have discovered that if asphaltic- hydrocar->e disposed of only as low grade fuel oils or as '
he least desirable raw stock for cracking proc
sses.
bons are brought into contact with rni'iltenîsub-- -f
stances or at any ratek with molten metals-orf
.alloys for a certain, short period of time, ata"
'
` In the cracking of the asphaltic- oils witha
.certain temperature.. they are ‘converted ‘into
"lew of producing lighter motor fuels, formation,
lubricating oils and I_,have discovered means of.
»f coke and noncondensabie gases soon sets in,
producing-and maintaining the necessary condi
:as oil or lubricating oils are used as starting ma
tical
1
esnlting in a yield of gasoline lower than what 30 _tions as regards the tirneelement,temperature.;-` " V
would be theoretically expected, taking into con
heat transfer, and contact, so that the reaction
lderation the hydrogen content of the original
can be maintained indefinitely or at least to suchV
an extent that such asprocess becomes of prac
tock. When overhead stocks such as kerosene,
value.
-
~
‘
l
`
`
l
»
.
'
The conversion _of asphaltic hydrocarbons. by
this process into lighter oils falling'malnly with-'
erial, a much more satisfactory decomposition
eaction ñrst takes place, but eventually asphalt
ormation sets in, resulting lultimately in th'e for
nation of coke and non_condensable gases, where
in the boiling point range of oils classed as lubri‘-,
eating oils, may be made highly efñcient; that is. l -
Iy valuable hydrogen is’lost.
side reactions producing undesirable by-products ' -« ' ~
-~
l,
In milder cracking operations, where effort is 40 ysuchaskflxed gases, coke- or other valueless or
detrimental products may .be largely suppressed 1;@
cade to convert residualv oils into fuel oil of
uwer viscosity, into oil stock more suitable for
to give a substantially complete yield of lighter '~
ntensive cracking operations, or even into lubri
oils on the basis of the asphalt converted. How- ‘
ating oil, the processes now known are capable 45 " ever, as the _time element is veryshortfit ls dim
f only partial conversion of asphalt, if the actu
cult _to establish and maintain conditionsab‘so'
l asphalt content of the stock is taken into con
lutely ideal as__regards every particle Iof'asphait>
'
lderatlon. Moreover, if recovery of lubricating
passing
being
that
througlì'the'reaction¿zonépthegresult"
part
of
the
asphalticfsubstance
re-„ml
'
ils or other valuable oil fractions is attempted as
separate distillate, a large part of the stock 60 mains unconver-ted in a singlepassaggfthrough
the process. This unconverted asph'azlt'fV~
not,
forked upon will remain as residue of less value
han the original stock and unilt for further
however, differ substantially from"the"'original
nnversion by the same process, except under
onditions where coke and gas formation takes
material and may in most instances be
by the same process, as by simply> returning it
lace.
‘
55 into the process with `fresh feed stock, or by treat.,
2
matassa
ing it separately. if necessary at a higher tem
short, is partly dependent on the exact nature
perature.
of the asphaltic oil stock worked upon. on the
temperature of the contact medium, on the tem
As stated, the necessary time element is very
perature of the incoming oil, etc. However, the
short. This is controlled in part at least by
keeping the amount of hydrocarbon material in 5 procedure necessary in each case will be made
clear from the disclosures given further on. In
the reaction zone to a minimum relative to the
available contact surface.v If the unconverted.
general, `the contact period should be sumciently
portion of the «asphalt is not removed almost
immediately, or within a certain time limit, de
pending on the temperature employed, it will
polymerize and eventually decompose with the
formation of carbon or coke, which carbonor
" short to insure that the hydrocarbon material.
typically unconverted asphalt, is not substan
tially decomposed into coke, nxed gas etc., auch
decomposition being prevented by removing the
coke will rapidly foul the contact medium or
metal bath, in many cases within a few minutes,
to such an extent that the converesion reaction
asphalt before it reaches excessive temperatures
or before substantial decomposition sets in due
to protracted contact at elevated temperatures;
orboth.
of asphalt into lubricating oil will be completely
arrested. despite the fact that the time element
and temperature might be suitable for converf
accomplished, first by introducing the asphalt or
oil containing it either upon the surface of the
The proper, short time element for contact is
metal bath or a- short distance below it, such as
sion.
Whether the molten substance, such ss molten
20 a few inches. and second by rapid or immediate
lremoval of the converted products from contact
with the bata by rapid or immediate veintiun
tion. induced by maintaining a sufilciently high
temperature in the molten bath and employing
metal or alloy. _called here’the contact medium.
acts in the process disclosed here in the _role of s
catalyst, isïnotcertain. 'As arule, the `reactions
produced by catalysis are >specific 'to certain sub
stances. whereas to my knowledge the conversion
reaction
here can be brought about by..
'any known means capable of( increasing the
volatility of the oils produced. such as 4vacuum
and/or carrier gases, but especially steam, inert
contact Íwith -any molten. substance. ,as far
as a substance is used lthat does not en--` v,
gases, and the like, which I have found most
effective and economical.
The use of steam or other eifective means of
and thus` make >it dimcult to determine the cause 50
of the reactions produced. At any rate, I have Y ‘ increasing volatility, is especially important from
ter into chemical Areaction with the asphaltv
successfully used tin, lead, and zinc, both singly
and in combination, one with another, and in
combination withantimony.
,
i
`
On the; other hand, therapidity 4with which
heat is;` transferable from the molten metal to ,
the small globules or iilms of asphalt material4
may be an important factor in the process. The
depolymerization or conversion reaction by which
asphaltis converted into lubricating oil may be
initiated at elevated temperatures, but is appar
ently endothermic in character, and a continued _
and rapid input'of heat is required to maintain
this reaction 1in ascendancy over undesirableA
side-reactions leading to degraded products, coke
the viewpoint of immediately removing any un- i
converted asphalt from contact with the bath. if
' temperaturesappreciatly above 400° C. are main
tained in the bath.V »If -temperatures below 400'`
C. are maintained in the bath; it is however pos
sible toallow theasphalt to remain in contact
ç with the bath a somewhat longer period, so that
it may be allowed to float on top of the bath and
is drained of! as rapidly as' possible. The steam
may be introduced into the molten bath at any
level, preferably at a lower ie'vei than the asphal
tic rawI stock. The steam does not decompose or
enter into reaction with the oil; the water re»
_' covered‘in the condensate is equal to the water
etc, Attempts to obtainthis rapid heat transfer ..
fed in as steam.
through poorly conducting surfaces. e. g.. solid
surfaces; wouldrequire such a high temperature
'I‘he feed stock need not be preheated when
temperatures appreciably over 400’ C. are main
.
surface ydeposition, of coke, thus defeating further
tained in the bath, but with lower temperatures.
preheating of the stock becomesV advisable; in
conversion. By the use of molten metal, however,
which case a preheat temperature of 'about 250° y
conversionsl at _a hydrocarbon temperature oi '
C.
version.
is sumcient
Due to
to the
insure
short
a high
contact
degree
period
of con-`
the -, ._ '
differential as to resultin local over-heating and
27_5’ to 375° C. may be maintained with a tem
temperature of the oil or oil vapors is' not brought `
peraturemmerential such for example that the
metal temperature need be only 450’ to 550’ C. ~ up to the temperature of the contact medium or
bath, in fact a contact period should be estab
The rapidity -Qf heat transfer is further aided by
the agitationxor circulation of the «molten metal. ' lished of only sumcient duration to heat the stock l
to a point where the convertedhproducts. and in
case- of higher temperatures in the bath also ï
the unconverted asphalt, are volatilized with the
aid ofsteam. Thetemperature of the vapors
for the more or less abrupt heatingofthe asphalt
to the desired'conversionj temperature;- L e.. t0 ' is usually around 300° C. It is to bestated here
that with a high temperature'in thebath, such as, 'c
avoid preheatingforfother pretreatment involv- `
for instance 450° C. and over,`a_ny unconverted
ing heating of thestcch` to elevated temperatures.>
Por example,- asphaltic' crude oils are sometimes 65 asphalt is readily volatillzed together with the
converted products, provided suilicient steam or
more amenable to conversion than are topped
other carrying gases and/or vacuum are used.
residual fractions obtained therefrom. In other
despite the fact that the temperature of the
instances, however, preheating of the conversion
vapors may not be over 300° C.- This volatiliza
stock immediately prior to conversion induces no
noticeable change and is of adi'. antage in reducing 70 tion of asphalt under such conditions may not be
due to actual z'aporization, butto mechanical
the heat load on> the molten metal.
To specify the actual time element necessary
carrying over, such as in the form of a fog.
I have found that in many instances my inven
for the asphalt lubricating cil reaction, that is.
tion may be advantageously practiced with the
to specify it in ruiaitsoi' time. is difficult, as the
contact timenecessary«fory conversion is .very
molten metal at a _temperamrepf 450°" to 550’
duction otthefheat is
.
1ny were. instances 1t u advantageous 'to provide _.
2,209,485
4
I claim ‘as-'my invention:
turning the heavy, asphaltic 'bottoms back into
the process with fresh feed stock. a complete
conversion of the asphalt present in the crude
oil was_aecomplished. >The converted distillate
or asphalt-tree, overhead therefrom could~be var
iously utilized The lubricating oil fractions were
equal or superior to thelubricating oil 'originally
associated with the crude, and also constituted
an excellent cracking stock‘ for liquid o_r vapor
phase cracking, as well as a blending stock for
fuel
oils.>
.
V
i
i
.
„
'
l . Example No. 2
The; same »crude oil _as-'in Example No. 1 was
treated kby passing it through' a molten alloy; con
i
1. A method of. converting asphaltic hydrocar
bon of the character ydescribed `to lubricating
oil, comprising‘the steps of: bringing said as
phaltic hydrocarbon into substantially momen
tary contact with a body of molten metal main
tained at such _a temperature in the range of 450°
to 550° C. that said asphaltic hydrocarbon will be
brought to a temperature within the range of
2‘75‘ to 375° C.; and dlsengaging the asphaltic
hydrocarbon and resulting converted products
brought to said temperature. from further con
tact with` the molten metal by-volatilization and
atomizaticn in a concurrent now of both volatil
ized' and nonvolatilized portions with `steam so
adjusted. that substantially no converted or un
-converted asphaltic hydrocarbon is left in con
tact with the molten metal for periods exceeding
the desired momentary contact.
sufiic'ientlyìî‘fiuidfatî‘all~î tunes;f . The. oil was' -pre
2. A method of converting asphaltic hydrocar
heated »tizsoë-chiiu introduced inte ,the .molten ,
>alloy tinches‘beiow the surface; The alloyrwaa ’ vbon ofthe character described t0 4lubricating oil
comprising the steps of: bringing said asphaltic
.kept -at a' temperature >of-3'10‘ C. and steam
hydrocarbon into substantially momentary con
.nmountign'i‘to -40% lof thejcrude 'was introduced
‘ through» another >-f’eed line; also 4' inches below ' tact with a body of molten metal maintained at
tlie___surface.‘f~Infthis case, due to the low tem‘ 25 such temperature that said asphaltic hydrocarbon
will be brought to a temperature within its tem
perature maintained in‘the alloy, the portion of
perature range of conversion as the result of
asphalt remainingv unconverted was’not volatil
Y
ized 'orfcarried-over by the vapors. but remained
said contact
with molten metal, whereby a sub
stantially complete conversion of asphaltic sub
on topbfíthe'alloy 'and »wascontinuously drained
sisting-o'l 80%.» of ~leadìandlofit of antimony, this
alloy having a' meltingpoint sufficiently far below
Vthe temperature ‘employed in'thlß‘ oase to keep it
out as'rapidly’asïpossible. «1 With-such a low‘tem- , 30 -stanceíto lubricating oil isV obtained without sub
-perature .inthe alloy. theasph’alt will ?otooke ‘ine stantial formation of coke, gas, or other reversion
products; and disengaging the asphaltic hydro
the-time required Vfor draining despite the. fact
carbon and resulting converted products'brought
that under such- conditionsit remains incontaot
with the bath a longer period thanincaseswhere ` to said temperature from further contact with the
the asphalt is removed by volatilization. The as 35 molten'metal by volatilization and atomization
_phalt or lresidue..drained on the surface of the ,_ in a concurrent flow of bothvolatilised and non
volatilized portions with steam so adjusted _that
. alloy amounted to 15% Aof theie‘rude oil treated.
The combined distillate` was'free .from asphalt.
'Bhe asphalt content was therefore reduced from
'11% m1569721;` . -No coke >or gas formation took place
and the totalfyield of voil and asphaltic residue
was 100%. It was found that the remaining
asphalt drained ofi the> surface yof the bath could
not be converted by ’returning itback into the
process with freshfee'd stock.;- However. »conver
sion of~ this residue was-accomplished-by employ
' lng a procedure. similar to theone given under
Example No.--1~and maintaining in the. bath a
temperature `of :about 550°' C. .
" “rxàmpleivd 3
An. Oklahoma 4crtule petroleum was used in this
substantially no converted Vor unconverted as
phaltic hydrocarbon is left in'contact with the
40 molten metalfor periods in excess of the desired
momentary contact.
‘
3. A process for converting asphaltic stock of
the character described into lubricating oil, com
prisingz' maintaining a body of molten metal in
a reaction zone at a temperature from about 375’
to about 550° C.; agitating said metal by `intro
ducing therein a stream of carrier gas and per
mitting said gasto escape from the upper surface
n of the metal; continuously bringing the asphaltic
w. stock into said reaction zone to contact the molten
metal at a level not lower than a few inches below
the upper surface of the metal; adjusting the
- stream of carrier gas to volatilize lubricating oil
case. l'I‘hisfcrude is extensively used for the
fractions present in the stock and formed by con
manufacture oflubricating oils, but contains 55
v version thereof to produce an' eiiiuent stream of
about 5% of asphalt and when distilled in the
gas andrhydrocarbon vapor having a temperature
ordinary. manner vproduces lubricating oil stocks
not greatly in excess of 300° C.; and continuously
which require .acid refining, with consequent
removing any non-‘volatile asphalt from the upper
heavy.losses,.-.«before they'can bennisbed to a
surface of the metal to prevent protracted con- '
proper c_olor with absorptive clays.
tact thereof with the molten metal.
distilledin a manner similar to theonegivenun
der Example No. '1, except that’sthe temperature
of theV lead bath was maintaineftlvat 4251"- C. and
the amount of steam usedïwfailáiil7a.> The yield
of oil recovered was.' approximately' „100% and no
carbon or coke formationfítooiì ace. The lubri
cating oil stock producedlwasthen_treated with
absorptive clays withoutjl “preliminary acid re
:ming 'and an ou witnîsîs ’haard _com was ob
60
4. A process as in claim_3 in which the' ‘asphaltic «
stock is introduced into the reaction zone at a
level not lower than four inches below the surface
of the molten metal. ' '
'
‘
’
i 5. A process for converting asphaltic stock of
65 lthe character described into lubricating oil, com
prising: maintaining a body of molten metal at a
temperature from about 375° to about 450° C.;
introducing the asphaltic stock into said metal at
tained, while the Alubriciaitn'ig 'oil' stock obtained
a depth of not over a few inches from the upper
from the same crude ’byßordi'?ary distillation 70 surface thereof; introducing a stream of carrier
methods could not be treated and finished with
gas into the body of molten metal to cause agi
absorptive clays without preliminary acid refining.
tation thereof and to aid in the volatilization oi
This application is a continuation-impart of
the lubricating oil; adjusting the relative rates of
my copending applications, Serial Nos. 142,560 76 introduction of asphaltic stock and carrier gas
and 166,307.
5
- 2,269,485
into the molten metal to cause complete and con
tinuous volatilization at temperatures not greatly
in excess of 300° C. of lubricating oil fractions
8. A method as in claim 'I in> which the stream
of carrier gas is adjusted to scavenge the surface
of the molten metal and maintain it substan
produced by conversion of the asphalt in the
tially clean, whereby the quantity of hydrocar
presence of the molten metal; and continuously
withdrawing non-volatile fractions accumulating 5 bon material in contact with the molten metal at
a given instant is minimized.
on the upper surface ofthe molten metal.
6. A process for converting asphaltic hydro
carbons into lubricating oil, comprising the steps
9. A method of converting asphaltic hydro
carbons of the character described into lubricat
ing oils, comprising: continuously bringing the
of: maintaining a body of molten metal in a re
action zone at a temperature from about 450° to l0 asphalticA hydrocarbons into contact with the sur
about 550° C.; passing a current of steam there
through; introducing the asphaltic hydrocarbon
into said reaction zone‘ at a level not lower than a
few inches below the surface of the molten metal
face of a body of molten metal; maintaining the
temperature of the metal above 450° C,; and re
moving'the converted and any unconverted hy
drocarbons from_ contact with the metal by
to contact the metal and induce at least partial l5` volatilization and atomization in a concurrent
conversion thereof into lubricating oil; and ad
ì i'low with a stream of a carrier gas so adjusted
that the temperature of the ellluent stream of v
vapor and gas does not substantially exceed
phalt and conversion products from the molten »
300° C.
metal in a concurrent stream of vapors and atom- ` 20
justing the current of steam to remove the as
ized particles.
l
7. A method of converting asphaltic hydro
carbons into lubricating oils, which comprises the
steps of: continuously bringing said asphaltic
1.0. A method of converting asphaltic hydro
carbons of the character described into lubricat
ing oil. which comprises: bringing the asphaltic
hydrocarbons continuously into contact with the
surface of a body of molten metal maintaining
hydrocarbons into contact with the surface of a
body of molten metal; maintaining the tempera 25 the temperature of the metal in a range from
ture ofthe metal in the range from about 450 to'
550° C.; and continuously disengaging the result
ing converted.` product and any unconverted hy
drocarbon >from contact with the molten metal by
volatilization4 and atomization in a concurrent 30
now of both volatilized and unvolatilized por-‘
tions with a stream of a carrier gas, so adjusted
that substantially no converted or unconverted
hydrccarbons are left in contact with the molten 35
metal beyond a momentary period.
about 350° C. to 450° C.; agitating said metal with
a current of carrier gas adjusted to produce an
emuent stream comprising gas and hydrocarbon
vapor, the temperature of said stream being not
greatly in excess of 300° C.; and continuously re
moving any non volatile asphalt from the upper
surface of the metal to prevent protracted con
tact thereof with the molten metal.
VAINO A. BALMI.
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